1. Field of the Invention
The present invention relates to thermoset polymers modified with certain fluorocarbon additives.
2. Description of the Prior Art
It has recently been proposed to modify thermoplastic polymers by incorporating therein various oils, gums, etc.
U.S. Pat. No. 3,485,787 discloses that certain block copolymers may be extended by incorporating mineral oil therein.
U.S. Pat. No. 3,830,767 teaches that bleeding of the extending oil from the block copolymer may be prevented by incorporating a petroleum hydrocarbon wax therein.
U.S. Pat. No. 4,123,409 relates to block copolymers having thermoplastic terminal blocks and an elastomeric intermediate block. The patent discloses blending with the copolymer a high molecular weight oil which is compatible with the elastomeric block portion of the copolymer. Where the elastomeric portion is a hydrocarbon, the oil employed is a mineral oil. Where the elastomeric block is a polysiloxane, a silicone oil is blended therewith.
U.S. Pat. No. 3,034,509 discloses the addition of silicone oil to polyethylene for use as surgical tubing.
U.S. Pat. No. 4,386,179 discloses the dispersion of a polysiloxane throughout an elastomeric thermoplastic hydrocarbon block copolymer.
Japanese Patent No. 60-104,161 describes an anti-friction composite material comprising certain resins and more than 1.0% by weight of a fluorocarbon oil which have been injected molded together in a manner such that the oil exudes onto the molded surfaces of the resin due to poor compatibility of the oil with the resin and differences in viscosity between the resin and oil to produce an anti-friction surface.
European Patent Application No. 222,201 published May 20, 1987, discloses the use of certain perfluoropolyethers as additives in rubber blends vulcanizable with peroxides.
U.S. Pat. Nos. 5,143,963, 5,128,773 and 5,912,291 disclose compositions of matter formed by melt-blending a thermoplastic polymer and from 0.01% to  less than 1.0% of a fluorocarbon additive.
There is continuing research leading to the development of novel polymeric materials, the properties of which are tailored by incorporating therein various additives.
It is an object of the present invention to provide novel thermoset polymer compositions having unique properties and which find utility in a wide variety of applications.
It is another object of the invention to provide a novel method for preparing thermoset polymer compositions having properties and characteristics heretofore unattainable.
These and other objects are realized by the present invention, one embodiment of which relates to a mixture comprising (1) a cross-linkable thermosetting resin providing composition and intimately admixed therewith, (2) from about 0.01 to about  less than 1.0%, by weight, based on the weight of the mixture, of a fluorocarbon additive selected from the group consisting of a fluorocarbon oil, a fluorocarbon gum, a fluorocarbon grease and mixtures thereof, the fluorocarbon additive having a lower surface energy than that of the thermoset resin formed by cross-linking the composition. Where the thermoset resin is other than a phenolic or unsaturated polymer resin, the amount of fluorocarbon additive may range from about 0.01 to about 5%, by weight based on the weight of the mixture.
A second embodiment of the invention concerns a method of forming a composition of matter comprising a cross-linked thermoset resin and from about 0.01% to about  less than 1.0% by weight, of a fluorocarbon additive selected from the group consisting of a fluorocarbon oil, a fluorocarbon gum, a fluorocarbon grease and mixtures thereof, the fluorocarbon additive having a lower surface energy than that of the resin, said method comprising intimately admixing the fluorocarbon additive with a cross-linkable thermosetting resin providing composition (I) for a time sufficient to produce a substantially homogeneous admixture comprising the resin and the fluorocarbon additive, followed by subjecting the mixture to conditions which provide a cross-linked thermoset solid resin wherein the concentration of the fluorocarbon additive through a cross-section of the solid resin composition is lower in the interior thereof and higher at the surfaces thereof. Where the thermoset resin is other than a phenolic or unsaturated polymer resin, the amount of fluorocarbon additive may range from about 0.01 to about 5%, by weight based on the weight of the mixture.
A further embodiment of the method of the invention is a method according to claim 8 including the preliminary step of forming a premix consisting of a fractional portion of the composition (I), in particulate form substantially uniformly wetted with the fluorocarbon additive and mixing the wetted first fraction with the remainder of the composition (I).
A still further embodiment of the invention is a composition of matter comprising (1) a cross-linked thermoset resin and (2) from about 0.01% to about  less than 1.0%, by weight, based on the weight of the composition of a fluorocarbon additive selected from the group consisting of an oil, gum, grease and mixtures thereof, the additive having a lower surface energy than that of the resin, wherein the concentration of the additive through a cross-section of the solid resin composition is lower in the interior thereof and higher at the surfaces thereof. Where the thermoset resin is other than a phenolic or unsaturated polymer resin, the amount of fluorocarbon additive may range from about 0.01 to about 5%, by weight based on the weight of the mixture.